CN108970353A - A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia - Google Patents

A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia Download PDF

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CN108970353A
CN108970353A CN201810778247.4A CN201810778247A CN108970353A CN 108970353 A CN108970353 A CN 108970353A CN 201810778247 A CN201810778247 A CN 201810778247A CN 108970353 A CN108970353 A CN 108970353A
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denitration
ammonia
flue gas
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CN108970353B (en
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宋华
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Xi'an Huada Sunny Green Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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Abstract

A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia, is passed through desulphurization denitration equipment after catalysis flue gas is mixed with sour gas containing ammonia according to volume flow ratio for 100-800:1, carry out desulphurization denitration；Poisonous and harmful group be wherein catalyzed in flue gas is divided into sulfur dioxide and nitrogen oxides；Wherein, the concentration of sulfur dioxide is 100-600mg/nm3, the concentration of nitrogen oxides is 150-200mg/nm3.This method will contain ammonia sour gas and mix with catalysis flue gas, and by low temperature SCR denitration, the desulphurization denitration to gaseous mixture is realized in the ammonia process of desulfurization and three parts of depriving hydrogen sulphide.Using the nitrogen oxides and sulfur dioxide in the ammonia component removing catalysis flue gas in sour gas containing ammonia, without additional addition denitrifying oxide agent.Dexterously by mixing two kinds of exhaust gas, realize turns waste into wealth synthesis desulfurating method of denitration provided by the invention, and has energy conservation and environmental protection, feature at low cost, easy to operate.

Description

A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia
Technical field
The invention belongs to oil refining the field of tail gas treatment, in particular to a kind of synthesis for being catalyzed flue gas and the sour gas containing ammonia Desulfurization denitration method.
Background technique
During oil refining, the catalysis flue gas containing a large amount of pernicious gases and sour gas containing ammonia can be generated.Wherein, it urges The main toxic, harmful components for changing flue gas are sulfur dioxide and nitrogen oxides.Sour gas containing ammonia is mainly by ammonia and hydrogen sulfide group At.It could be discharged after needing that these four components are effectively treated.
In terms of nitrogen oxides control, main more mature technology is selective catalytic reduction (SCR), selection at present Property noncatalytic reduction (SNCR), electronic beam method and red-hot carbon reduction etc. technologies.Wherein SCR is that absolutely mainstream is also at present It is commercialized gas denitrifying technology the most successful.This method needs under the effect of the catalyst, by adding reducing agent (such as ammonia Deng), nitrogen oxides is reduced into the nitrogen of environmental sound.
And the removing sulfuldioxide of sulfur dioxide mainly has the desulfurization of calcium method, magnesium processes desulfurization and the ammonia process of desulfurization.These sulfur methods Principle is substantially similar.It is reacted by addition oxide or ammonium hydroxide with sulfur dioxide, generates sulphite.Leading to oxygen-containing gas again will be sub- Oxide sulfate is at sulfate.Wherein, the desulfurization of calcium method and magnesium processes desulfurization can generate the waste water of high rigidity.In contrast, ammonia process is de- Sulphur has the advantages that easy to operate, desulfurization effect is good, by-product high financial profit.
Therefore, the tail gas treatment process of mainstream is needed when removing is catalyzed the nitrogen oxides and sulfur dioxide in flue gas at present Ammonia or ammonium hydroxide are additionally added, the increase of processing cost is caused.
For the sour gas containing ammonia containing hydrogen sulfide, the method for mainstream is Claus method at present.This method is by will be acid Gas mixes with air, and carries out imperfect combustion, is elemental sulfur and sulfur dioxide by Oxidation of Hydrogen Sulfide, and ammonia will be converted into nitrogen Gas or nitrogen oxides.This method reaction temperature is high, and energy consumption is high, and needs to the sulfur dioxide and nitrogen oxides of generation Reason.Another method is the desulfurizing agent by adding containing metal oxide, to handle the hydrogen sulfide in sour gas containing ammonia.But due to The concentration of the sour gas containing ammonia is usually larger, under higher concentration of hydrogen sulfide, is extremely difficult to higher desulfurization effect, and desulfurizing agent It will be unable to regenerate.It needs to handle the ammonia in sour gas containing ammonia simultaneously, processing cost is high.
Summary of the invention
It is an object of the invention in view of the above shortcomings of the prior art, provide a kind of catalysis flue gas and sour gas containing ammonia Synthesis desulfurating method of denitration, it is easy to spread that the preparation method has a simple process, this method can under mild reaction conditions, take off Except the nitrogen oxides in catalysis flue gas and sour gas containing ammonia, sulfur dioxide, hydrogen sulfide and ammonia.
In order to achieve the above objectives, the present invention, which adopts the following technical scheme that, is achieved:
A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia, will catalysis flue gas and sour gas containing ammonia according to Volume flow ratio is to be passed through desulphurization denitration equipment after 100-800:1 is mixed, and carries out desulphurization denitration.
A further improvement of the present invention lies in that poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides； Wherein, the concentration of sulfur dioxide is 100-600mg/nm3, the concentration of nitrogen oxides is 150-200mg/nm3。
A further improvement of the present invention lies in that poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia；Wherein, The mass fraction of hydrogen sulfide is 10%-60%, and the mass fraction of ammonia is 10%-25%.
A further improvement of the present invention lies in that the method used when denitration is low-temperature selective catalytic reduction method, reaction is warm Degree is 80-180 DEG C.
A further improvement of the present invention lies in that used method is the ammonia process of desulfurization when scrubbing CO_2.
A further improvement of the present invention lies in that ammonium hydroxide used is partly or entirely by pure when using ammonia process removal sulfur dioxide Ammonia in water and sour gas containing ammonia is made；Ammoniacal liquor mass concentration is 15%-20%.
A further improvement of the present invention lies in that when removing hydrogen sulfide, using iron oxide process or zinc oxide method, preferably iron oxide Method.
A further improvement of the present invention lies in that when carrying out hydrogen sulfide stripping using iron oxide process, the desulfurizing agent saturation of use It is regenerated afterwards using air or oxygen.
A further improvement of the present invention lies in that being regenerated after the desulfurizing agent saturation of use using air；And using empty When gas is regenerated, regeneration temperature is 70-100 DEG C, preferably 80 DEG C.Reproduction time is 3-5 hours.
A further improvement of the present invention lies in that after desulfurizer regeneration, with the sulphur simple substance of extractant extraction surface.
A further improvement of the present invention lies in that extractant is benzene, toluene, diesel oil, carbon tetrachloride or carbon disulfide, preferably bavin Oil.
Compared with prior art, the invention has the benefit that
1, desulphurization denitration cost reduces: the present invention is mixed by that will be catalyzed flue gas with sour gas containing ammonia, using containing propylhomoserin Property gas in ammonia carry out the removing of nitrogen oxides and sulfur dioxide, without additional addition ammonia or ammonium hydroxide.Meanwhile shape after mixing At mixed gas in concentration of hydrogen sulfide decline to a great extent, reduce the removing pressure of hydrogen sulfide.In lower concentration of hydrogen sulfide Under, desulfurizing agent can be regenerated after saturation.Therefore, this process flow avoids the addition of ammonia and ammonium hydroxide, extends de- The service life of sulphur agent, significantly reduces operating cost.
2, hydrogen sulfide stripping effect promoting: the present invention is mixed by that will be catalyzed flue gas with sour gas containing ammonia, is made in exhaust gas Concentration of hydrogen sulfide drops to 2,000ppm or so from about 500,000ppm, reduces the removing pressure of hydrogen sulfide.In lower sulphur Change under hydrogen concentration, the desulfurization effect of desulfurizing agent can be promoted.Synthesis desulfurating method of denitration provided by the invention is dexterously by by two Kind exhaust gas mixing, realizing turns waste into wealth, and has energy conservation and environmental protection, feature easy to operate.
Further, the present invention can produce the by-product of high economic value, including ammonium hydroxide, ammonium sulfate and sulfur in lump form.
Further, the hydrogen sulfide in gaseous mixture is removed by iron oxide or zinc oxide method, and is extracted and produced by diesel oil By-product sulfur in lump form.By mixing two kinds of exhaust gas, it is useless dexterously to realize change for synthesis desulfurating method of denitration provided by the invention For treasured, and there is energy conservation and environmental protection, feature at low cost, easy to operate.
Further, hydrogen sulfide stripping is carried out using iron oxide process, it is at low cost.
Detailed description of the invention
Fig. 1 is the synthesis desulfurating method of denitration flow chart of catalysis flue gas and the sour gas containing ammonia of the invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
In the present invention, before catalysis flue gas is mixed with sour gas containing ammonia, the temperature for being catalyzed flue gas is 80-200 DEG C.
Embodiment 1
Referring to Fig. 1, the present invention the following steps are included:
I, exhaust gas mixing and low temperature SCR denitration:
1) catalysis flue gas is mixed with sour gas containing ammonia.
2) before mixing, catalysis flue gas flow is 71200Nm3/ h, temperature are 200 DEG C.Wherein, sulfur dioxide concentration is 490mg/m3, nitrous oxides concentration 186mg/m3, remaining component is on this process without influence.
3) before mixing, throughput containing propylhomoserin is 150Nm3/ h, temperature are 90 DEG C.Wherein, hydrogen sulfide mass fraction is 0.4902, ammonia mass fraction is 0.2163, remaining component is on this process without influence.
4) after mixing, mixed gas flow 71343Nm3/ h, temperature are 199.8 DEG C.Sulfur dioxide concentration is 489.0mg/ m3, nitrous oxides concentration 185.6mg/m3, concentration of hydrogen sulfide 1099.0mg/m3, ammonia concentration 514.7mg/m3。
5) gaseous mixture is first passed through to dust-extraction unit to be dusted.
6) after dedusting, gaseous mixture is passed through Benitration reactor, and reaction temperature is 180 DEG C.It is filled in Benitration reactor Three layers of catalyst.Flue gas passes through catalyst bed and carries out denitration.After the completion of denitration, nitrous oxides concentration 37mg/ m3。
7) residual gas is passed through ammonia process of desulfurization unit and carries out step II.Wherein, ammonia process of desulfurization unit includes heat exchanger, desulfurization Device and absorber.
II, the ammonia process of desulfurization:
1) sulfurous gas is first passed through heat exchanger, exchanges heat with the ammonium sulfate of low temperature, is cooled to 80 DEG C.
2) gas after cooling squeezes into the solution of devulcanizer bottom.Sulfur dioxide in bubbling by with the hydration ammonia in solution Reaction, and generate ammonium sulfite.
3) ammonium hydroxide will pass through the atomizing lance of absorber inner wall from absorber overhead, enter absorption with the drop of small size Device, and reacted with the sulfur dioxide escaped from solution, finally flow into the solution of devulcanizer bottom.
4) and after the ammonium hydroxide drop contact on absorber upper layer, residual gas (i.e. containing the sour gas of hydrogen sulfide) can be passed through sulphur Change hydrogen removing means, carries out step III.
5) the ammonium sulfite solution of devulcanizer bottom will flow into oxidation reactor.Oxidizing temperature is 50 DEG C.Ammonium sulfite quilt The air oxidation being passed through simultaneously is ammonium sulfate.
6) ammonium sulfate is concentrated, heat exchanger is first passed through before concentration and high-temperature gas exchanges heat, is warming up to 80 DEG C.
7) ammonium sulfate is further heated up to 110 DEG C, ammonium sulfate is concentrated.
8) ammonium sulfate after being concentrated obtains ammonium sulfate slurries through supercooling after crystallization.
9) ammonium sulfate slurries are separated by solid-liquid separation by centrifugation, and drying and other steps are finally made ammonium sulfate product.
10) isolated liquid is ammonia spirit, can be recycled to ammonia water tank and reuses.
III, iron oxide process depriving hydrogen sulphide:
1) ferric oxide desulfurizer is loaded into hydrogen sulfide absorption device.
2) lead to nitrogen and replace remaining hydrogen sulfide gas.
3) sour gas containing hydrogen sulfide will be passed through from absorber bottom, can be from absorber after peroxide of iron bed Top discharge.Wherein, absorbing temperature is 40 DEG C；Air speed is 600h-1。
4) iron oxide can be reacted with hydrogen sulfide generates iron sulfide.Iron bed to be oxidized detects hydrogen sulfide close to when being saturated Exit concentration has obvious rising.Sour gas is switched into another absorber that fresh desulfurizing agent is housed.
5) desulfurizing agent need to be regenerated, is passed through air as regeneration gas from absorber bottom.
6) regeneration initial stage keeps 100h-1Low-speed.After low-speed is kept for 1 hour, air speed is improved to 500h-1, after 5 hours of continuous regeneration.Regenerative process whole process is kept for 80 DEG C.
7) after regenerating, sulphur is cemented out in the form of sulphur simple substance by oxygen, and is attached to desulfurizing agent surface.From devulcanizer top Portion flows into diesel oil extraction.
8) desulfurizing agent bed need to be all immersed in diesel oil, impregnate 2 hours.Soaking process need to be stirred.
9) after extracting, the diesel oil dissolved with sulphur simple substance need to be filtered, to remove croci in diesel oil.
10) diesel oil is cooled to 15 DEG C after, and is filtered.
11) filter residue filtered can be made into sulphur brick.Diesel fuel filter liquid stream is back to spare in diesel fuel tank.
Embodiment 2
The synthesis desulfurating method of denitration of catalysis flue gas and the sour gas containing ammonia of the invention are as follows:
Poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides；And the concentration of sulfur dioxide is 100mg/nm3, the concentration of nitrogen oxides is 200mg/nm3.Poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia； And the mass fraction of hydrogen sulfide is 10%, and the mass fraction of ammonia is 25%.
It is passed through desulphurization denitration equipment after catalysis flue gas is mixed with sour gas containing ammonia according to volume flow ratio for 800:1, is adopted Denitration is carried out at being 100 DEG C in reaction temperature with low-temperature selective catalytic reduction method；Then ammonia process of desulfurization removal sulfur dioxide is adopted, In, when removal sulfur dioxide, ammonium hydroxide used is partly or entirely made by pure water and the ammonia in sour gas containing ammonia；Ammonium hydroxide quality is dense Degree is 15%.After removal sulfur dioxide, depriving hydrogen sulphide is carried out using iron oxide process, and hydrogen sulfide stripping is carried out using iron oxide process When, the desulfurizing agent of use is regenerated after being saturated using air.After desulfurizer regeneration, with the sulphur simple substance of extractant extraction surface, Wherein, extractant is benzene.
Embodiment 3
The synthesis desulfurating method of denitration of catalysis flue gas and the sour gas containing ammonia of the invention are as follows:
Poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides；And the concentration of sulfur dioxide is 300mg/nm3, the concentration of nitrogen oxides is 180mg/nm3.Poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia； And the mass fraction of hydrogen sulfide is 60%, and the mass fraction of ammonia is 20%.
It is passed through desulphurization denitration equipment after catalysis flue gas is mixed with sour gas containing ammonia according to volume flow ratio for 300:1, is adopted Denitration is carried out at being 80 DEG C in reaction temperature with low-temperature selective catalytic reduction method；Then ammonia process of desulfurization removal sulfur dioxide is adopted, In, when removal sulfur dioxide, ammonium hydroxide used is partly or entirely made by pure water and the ammonia in sour gas containing ammonia；Ammonium hydroxide quality is dense Degree is 17%.After removal sulfur dioxide, depriving hydrogen sulphide is carried out using iron oxide process, when carrying out hydrogen sulfide stripping using iron oxide process, It is regenerated after the desulfurizing agent saturation of use using oxygen.After desulfurizer regeneration, with the sulphur simple substance of extractant extraction surface, In, extractant is toluene.
Embodiment 4
The synthesis desulfurating method of denitration of catalysis flue gas and the sour gas containing ammonia of the invention are as follows:
Poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides；And the concentration of sulfur dioxide is 500mg/nm3, the concentration of nitrogen oxides is 170mg/nm3.Poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia； And the mass fraction of hydrogen sulfide is 30%, and the mass fraction of ammonia is 10%.
It is passed through desulphurization denitration equipment after catalysis flue gas is mixed with sour gas containing ammonia according to volume flow ratio for 100:1, is adopted Denitration is carried out at being 180 DEG C in reaction temperature with low-temperature selective catalytic reduction method；Then ammonia process of desulfurization removal sulfur dioxide is adopted, In, when removal sulfur dioxide, ammonium hydroxide used is partly or entirely made by pure water and the ammonia in sour gas containing ammonia；Ammonium hydroxide quality is dense Degree is 18%.After removal sulfur dioxide, depriving hydrogen sulphide is carried out using zinc oxide method.
Embodiment 5
The synthesis desulfurating method of denitration of catalysis flue gas and the sour gas containing ammonia of the invention are as follows:
Poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides；And the concentration of sulfur dioxide is 600mg/nm3, the concentration of nitrogen oxides is 150mg/nm3.Poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia； And the mass fraction of hydrogen sulfide is 40%, and the mass fraction of ammonia is 15%.
It is passed through desulphurization denitration equipment after catalysis flue gas is mixed with sour gas containing ammonia according to volume flow ratio for 600:1, is adopted Denitration is carried out at being 150 DEG C in reaction temperature with low-temperature selective catalytic reduction method；Then ammonia process of desulfurization removal sulfur dioxide is adopted, In, when removal sulfur dioxide, ammonium hydroxide used is partly or entirely made by pure water and the ammonia in sour gas containing ammonia；Ammonium hydroxide quality is dense Degree is 20%.After removal sulfur dioxide, depriving hydrogen sulphide is carried out using iron oxide process, and hydrogen sulfide stripping is carried out using iron oxide process When, the desulfurizing agent of use is regenerated after being saturated using air.After desulfurizer regeneration, with the sulphur simple substance of extractant extraction surface, Wherein, extractant is diesel oil.
Embodiment 6
The synthesis desulfurating method of denitration of catalysis flue gas and the sour gas containing ammonia of the invention are as follows:
Poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides；And the concentration of sulfur dioxide is 200mg/nm3, the concentration of nitrogen oxides is 190mg/nm3.Poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia； And the mass fraction of hydrogen sulfide is 50%, and the mass fraction of ammonia is 23%.
It is passed through desulphurization denitration equipment after catalysis flue gas is mixed with sour gas containing ammonia according to volume flow ratio for 500:1, is adopted Denitration is carried out at being 120 DEG C in reaction temperature with low-temperature selective catalytic reduction method；Then ammonia process of desulfurization removal sulfur dioxide is adopted, In, when removal sulfur dioxide, ammonium hydroxide used is partly or entirely made by pure water and the ammonia in sour gas containing ammonia；Ammonium hydroxide quality is dense Degree is 20%.After removal sulfur dioxide, depriving hydrogen sulphide is carried out using iron oxide process, and hydrogen sulfide stripping is carried out using iron oxide process When, the desulfurizing agent of use is regenerated after being saturated using air.After desulfurizer regeneration, with the sulphur simple substance of extractant extraction surface, Wherein, extractant is carbon tetrachloride.
The present invention is to utilize institute in sour gas containing ammonia by mixing the sour gas containing ammonia of high concentration with catalysis flue gas first The ammonia contained reacts in low-temperature SCR unit with nitrogen oxides.Meanwhile the concentration of hydrogen sulfide is greatly reduced in gaseous mixture, this has Effect alleviates the operating pressure of subsequent process, and improves desulfurization precision.
After removing nitrogen oxides, sulfur dioxide is removed by the ammonia process of desulfurization is carried out.Ammonium hydroxide can generate sulfurous with sulfur dioxide Acid ammonium solution.It can be ammonium sulfate by sulfite oxidation by way of being passed through oxygen-containing gas.Ammonium sulfate slurries pass through subsequent Concentration is centrifugated, and after drying and other steps, ammonium sulfate product can be obtained.Ammonium sulfate is a kind of excellent nitrogenous fertilizer.
After the ammonia process of desulfurization, the main component hydrogen sulfide in exhaust gas will be removed by iron oxide process or zinc oxide method.Iron oxide It can be reacted with hydrogen sulfide and generate iron sulfide.After iron to be oxidized is completely converted into iron sulfide, oxygen-containing gas is passed through bed and is carried out Iron oxide regenerates, and the sulphur in iron sulfide will be replaced out in the form of elemental sulfur.Elemental sulfur can be extracted agent extraction, as sulphur Sulphur uses.Tail gas after processing can direct emission.
SCR method employed in the present invention is low-temperature SCR method.Low temperature (80-180 DEG C) continuous denitration may be implemented.
Ammonia process of desulfurization scrubbing CO_2 is selected in the present invention.Wherein, the ammonia that can be added in pure water dissolution exhaust gas is made Ammonium hydroxide.
The ammonium sulfite generated during sulfur dioxide removal in the present invention can be oxidized to ammonium sulfate.By being concentrated, from The heart separates, and after drying and other steps, can be made into ammonium sulfate product, the by-product as this process flow.
When removing hydrogen sulfide in the present invention, used desulfurizing agent is iron oxide, zinc oxide or copper oxide.Iron oxide desulfurization Effect is good, at low cost, preferably iron oxide.
Process flow of the invention is matched altogether there are two hydrogen sulfide absorption device.When one of absorber saturation, can be switched To another absorber.Meanwhile saturable absorber is regenerated.
In the present invention in hydrogen sulfide removal process, gas enters from absorber bottom, air speed 500-2000h-1.It is preferred that 800- 1500h-1.Operation temperature is 20-40 DEG C.
In the present invention when regenerator iron oxide desulfurizing agent, the oxygen-containing gas used is air.Regeneration temperature is 70-100 DEG C, excellent Select 80 DEG C.Reproduction time is 3-5 hours.
The sulphur that recycling obtains can be carried out the sequence of operations such as to separate in the present invention, be finally made sulphur brick product, as The by-product of this process flow.
The present invention will contain ammonia sour gas and mix with catalysis flue gas, by low temperature SCR denitration, the ammonia process of desulfurization and depriving hydrogen sulphide three The desulphurization denitration to gaseous mixture is realized in a part.Utilize the nitrogen oxygen in the ammonia component removing catalysis flue gas in sour gas containing ammonia Compound and sulfur dioxide, without additional addition denitrifying oxide agent, and can coproduction by-product ammonium hydroxide and ammonium sulfate.In gaseous mixture Hydrogen sulfide then passes through iron oxide or zinc oxide method removing, and extracts production by-product sulfur in lump form by diesel oil.It is provided by the invention Dexterously by mixing two kinds of exhaust gas, realize turns waste into wealth synthesis desulfurating method of denitration, and has energy conservation and environmental protection, cost Low, easy to operate feature.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia, it is characterised in that: by catalysis flue gas and contain ammonia Sour gas is to be passed through desulphurization denitration equipment after 100-800:1 is mixed according to volume flow ratio, carries out desulphurization denitration.
2. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 1, feature exist In: poisonous and harmful group in catalysis flue gas is divided into sulfur dioxide and nitrogen oxides；Wherein, the concentration of sulfur dioxide is 100- 600mg/nm3, the concentration of nitrogen oxides is 150-200mg/nm3。
3. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 1, feature exist In: poisonous and harmful group in sour gas containing ammonia is divided into hydrogen sulfide and ammonia；Wherein, the mass fraction of hydrogen sulfide is 10%-60%, The mass fraction of ammonia is 10%-25%.
4. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 1, feature exist In: for the method used when denitration for low-temperature selective catalytic reduction method, reaction temperature is 80-180 DEG C.
5. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 1, feature exist In: when removal sulfur dioxide, used method is the ammonia process of desulfurization.
6. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 5, feature exist In: when using ammonia process removal sulfur dioxide, ammonium hydroxide used is partly or entirely made by pure water and the ammonia in sour gas containing ammonia；Ammonia Water quality concentration is 15%-20%.
7. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 1, feature exist In: when depriving hydrogen sulphide, using iron oxide process or zinc oxide method.
8. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 7, feature exist In: when carrying out hydrogen sulfide stripping using iron oxide process, regenerated after the desulfurizing agent saturation of use using air or oxygen.
9. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 8, feature exist In: after desulfurizer regeneration, with the sulphur simple substance of extractant extraction surface.
10. a kind of synthesis desulfurating method of denitration for being catalyzed flue gas and the sour gas containing ammonia according to claim 9, feature exist In: extractant is benzene, toluene, diesel oil, carbon tetrachloride or carbon disulfide.
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